Flotation oil



number of different Patented Mar. 24, 1925. V

UNITED STATES BOZBERT.M. ISHAM, OF OKMULGEE, OKLAHOMA, ASSIGNOB, BY MESNE ASSIGNMENTS,

TO SETH B'. HUNT, TRUSTEE, 0F MOUNT KISCO,

NEW YORK.-

FLOTATION OIL.

1T0 Drawing.

To all whom z'tmayconcern:

Be it known that I, ROBERT citizen of the United States of America, residing at Okmulgee, in the county of Okmulgee, State of Oklahoma, have invented certain new and useful Improvements in Flotation Oils; and I do hereby declare the following to be a full, clear, exact description of the invention, such as Will enable others skilled in the art to which it appertains to make and use the same.

This invention relates to flotation oils and more particularly to a method of concentrating ores by froth flotation and reagents for roducing the flotation froth.

The well-linown flotation process of concentrating ores consists in separating metalliferous matter, particularly metallic sulphides, from the gangue of the ore. By this process pulverized 'ore is thoroughly mixed with water containing a small amount of a frothing agent, and the mixing is so conducted as to thoroughly aerate the mixture to coat the metalliferous matter with air bubbles and to form a froth. The froth carries the metal and may be readily separated from the Water carrying the gangue to recover the metal. A large kinds of frothing agents have been used for floating metalliferous matter, and it has been found that different kinds of metals and ores require different kinds and quantities of frothing agents. A careful study of the physical phenomena involved in the flotation of metallic matter shows that two distinct properties are re uired of a flotation oil to obtain the deslred results :First, a portion of the oil must be dissolved in water an act to diminish the surface tension of the water, and second, a part of the oil must remain undissolved and act to coat the surface of the metallic particles to float and collect them.

The primary object of the present invention is to provide a flotation oil which has desirable properties for making a full and elficient separation of the metalliferous matter from the gangue of the ore.

Another object of the invention is to provide a flotation oil which may be modified readily to be adapted for the various kinds of ore, and fortreating other products by flotation processes.

With these and other objects in view, the

Application filed December 17, 1921.

M. IsHAM, a I

and

a tifying treating any of Serial 1T0. 523,205.

invention consists in the improved flotation oils hereinafter described and particularly defined in the claims.

In the copending application of Sidney Born and Robert M. Isham, Serial No. 294,013, filed May 1, 1919, for process of producing alcohols, is described a process by which alcohols, polymerized olefines, alkyl hydrogen sulphates and other products can be manufactured from oil gas. In accordance with this process, oil gas which preferably is obtained by cracking oil under pressure, is scrubbed under pressure by a countercurrent circulation with a solution containing concentrated sulphuric acid and alkyl hydrogen sulphates. By this scrubbin operation the olefines are selectively sulp ated at different temperatures. The higher ,olefines such as hexylene, and butylene, are-absorbed at temperatures below 0 C. The propylene is absorbed at a temperature of about 20 C. and theethylene is absorbed at a temperature ofabout 80 to 90 C; The acid liquor delivered from the absorbers contains alkyl hydrogen sul-. phates, sulphuric acid, polymerized olefines and diolefines, saturated and unsaturated hydrocarbons. The condensed unabsorbed hydrocarbons are not miscible in the acid liquid andmay be separated therefrom by gravity separation. By diluting the acid liquid with water the alkyl hydrogen sulphates are partially hydrated and the polymerized unsaturated hydrocarbons are set free and may be separated therefrom by a gravity separation. The hydrolyzation of the acid liquid may be completed in a fractionating still and by properly fractionating and recthe said liquid, the various alcohols may be collected separately. Also groups or mixtures of alcohols may be collected by appropriate fractional distillation.

The lymerized unsaturated hydrocarbons obtained by the rocess outlined above are collected in the orm of an oil which has a dark green or brown color which is opalescent. This oil is not a tar and does not ordinarily contain tar. In this respect it may be clearly distinguished from the slud e that is recovered in the ordinary metho s of treating etroleum distillates with concentrated sul huric acid at ordinary temperatures to ecolorize and deodorize them. The oil contains polymerized sim 1e and higher olefines, polymerized diole es or amylene unsaturated hydrocarbons with two double linkings, polymerized acetylene or hydrocarbons with triple linkings, and some other unsaturated hydrocarbons. The percentage composition of the various types of unsaturated hydrocarbons in the polymerized oil depends upon the character of the oil gas from which the oil is made. If the oil -is cracked under pressure at extremel high temperatures, a comparatively hi'g percentage of diolefines will be formed. If a large percentage of the diolefines is present,

the oil may contain some tars because the diolefines react so readily with concentrated sulphuric acid that it is diflicult to prevent the formation of tars. When oil is cracked at the comparatively lower temperatures and pressure, that is, 100 pounds pressure or lower, and 800 F. or lower, a' small amount of diolefines is formed in the oil gases, and these may be readily polymerized without the formation of tars. The polymerized oils formed from gases produced when cracking oil at the lower pressures and temperatures, contain a major portion of the polymerized simple olefi nes.

All of the oils described above which contain polymerized unsaturated hydrocarbons (hereinafter termed polymerized oils) ave remarkable collecting properties for selecting the metalliferous matter of the ore sary and coating it with an oily film in preference to coating the gangue. In addition to havin the collective property, it is necesor a successful flotation oil to have froth forming properties. With some forms of ores the polymerized oils willform very satisfactory froths, and can be used alone. With this purpose, the polymerized oil has been used of the weight of the ore being treated, and gives very satisfactory flotation results.

In order to obtain a maximum selective action between sulphide minerals and a 'gangue of the mineral, it is necessary to have the greatest possible difference between the properties of the water phase and the 'oil phase in the flotation system. The polymerized oil may be considered as practically insoluble in water; hence-it will produce the greatest possible difl'erence between water phase and the oil phase, and consequently give a greater selective action; In case where the polymerized oils do not produce a. satisfactory froth, it has been found that the addition of an alcohol will give this re sult, particularly the alkyl alcohols which are produce by the Born and Isham process outlined above.

examination of the various alcohols produced from oil gases shows that there is a steadily decreasing solubility with the increase in molecular weight and with the e from the tertiary to the secondary and then to the primary alcohols. The

1n the proportion of 1% to 1/20 aesaeee lighter alcohols, such as ethyl and pro yl alcohol can be considered as ractically fu l y soluble in water, while the heavier alcohols become lessand less soluble as their molecular weights increase.

Whena flotation oil, which is made up by polymerlzed oil and a heavy alcohol that is only slightly soluble in water, is used in a water menstruum, the alcohol will be distributed between the waterphase and the polymerized oil base. The greater the amount of alcoho associated with the water phase, the closer will be the similarity in the property of the oil and water phases, and the selective action of the polymerized oil will be relatively diminished. It will be seen therefore that by the use of the polymerized oil and alcohols which have different degrees of solubility in water, a flotation oil of practically any desired combination of selective and.(f1roth forming properties may be obtaine By means of the Born and Isham rocess of producing alcohols from oil gas, t e following more simple aliphatic alcohols may be produced; ethyl alcohol, secondary propyl, butyl, amyl, hexyl and heptyl alcohols, and tertiary, butyl, amyl, hexyl and heptylalcohols. Tests which have been made with these various alcohols have shown that'all of them except ethyl will produce a satisfactory froth for a flotation process. Further, there is a continuous increase in the depths of froth which will be formed by the alcohols as the molecular weights of the alcohol increase. It is not necessary that these aliphatic higher alcohols shall be produced by the Born and Isham process described above, and tests have been made with the commercial aliphatic higher alcohols which show that they produce very satisfactory froths. In wor ing out various combinations of alcohols with polymerized oils, it is found that the greater the molecular weight of the alcohols, the smaller is the proportion of the polymerized oil required goofider to produce the maximum depth of t i a Tests have shown that the higher aliphatic alcohols not only possess frothing properties for flotation oil, but also possess selective properties, and therefore the higher alcohols may be used alone and give a. satisfactory metal separation. For example, tertiary butyl and tertiary amyl alcoho s will give a satisfactory separation of the metal sulphides of the Z1110 sulphide ores. It is also oils wh ch have been sat fa to y u ed in g1ven examples of flotation matter of the s Iso propyl Tertiary Secondary secondary and tertiary amyl alcohols 1 part.

5. Polymerized oil 2/5 parts. Commercial iso butyl alcohol 1 part.

6. Polymerized oil 3/5 parts. Commercial secondary and tertiary alcohol 1 part. These flotation oils have been used in the ratio of 1/20 of one per cent to one per cent by weight of the ore being treated, the proportion of the flotation oil depending upon the character of the ore. It has also been found that the presence of an acid with metal. Therefore,

vjventing the angue the flotation oil will sometimes assist in prefrom being coated with the oil and t us allow the more effective in floating'the metalliferous a small amount of free sulphuric acid or been used with a flotation oil consisting of polymerized oil alone, or consisting of polymerized'oil with an alcohol or a mixture of alcohols, or consisting .of an alcohol alone or amixture of alcohols;

Although the invention has been described by reference to the use of polymerized unsaturated h drocarbon oils, and the various aliphatic alcohols which are particularly produced by the process of Born and Isham, the invention is not limited to the use of thepolymerized oils and alcohols produced by t is process, merized oils and aliphatic alcohols which are produced b any of the known processes may be use in making a flotation product.

The preferred form of the invention having been thus described, what is claimed as new 18:

' 1. As an article of manufacture an oil'- like product comprising a mixture of polymerized hydrocarbons and alcohol.

. cohol.

flotationoil to be alkyl sulphuric acid has but any of the various poly- 2. As -an article of manufacture an oillike product comprising a mixture of polymerized unsaturated hydrocarbons and al- 3. As an article of manufacture an oillike product comprising a mixture of polymerized hydrocarbons and higher aliphatic alcohol.

4. As an article of manufacture, an oillike product comprising a mixture of polymerized unsaturated hydrocarbons and a secondary alcohol.

.5. As an article of manufacture an oillike product comprising a mixture of polymerized unsaturated hydrocarbons and a mixture of secondary alcohols. 7

6. As an article of manufacture an oillike product comprising a mixture of polymerized unsaturated hydrocarbons and a tertiary alcohoh .7. 'As an article of manufacture an oillike product comprising a mixture of polymerized unsaturated hydrocarbons and a mixture of tertiary alcohols.

8. As an article of manufacture an oillike productcomprising a mixture of polymerized olefines and diolefines.

like product comprisin merized olefines and aliphatic alcohol.

10. As an article of manufacture an oila mixture of lyiolefines and higher hydrocarbon constituents:

In testimony whereof I aflix my si ature.

ROBERT M. IS

olefines and diol'efines, secondary 9. As an article of manufacture an oillike product comprising a mixture of poly- 'merized unsaturated an article of manufacture a flota- 

